CN113150243B - Dynamic self-healing antirust epoxy resin and preparation method thereof - Google Patents
Dynamic self-healing antirust epoxy resin and preparation method thereof Download PDFInfo
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- CN113150243B CN113150243B CN202110327617.4A CN202110327617A CN113150243B CN 113150243 B CN113150243 B CN 113150243B CN 202110327617 A CN202110327617 A CN 202110327617A CN 113150243 B CN113150243 B CN 113150243B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/12—Polycondensates containing more than one epoxy group per molecule of polycarboxylic acids with epihalohydrins or precursors thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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Abstract
A dynamic self-healing antirust epoxy resin and a preparation method thereof are provided, disulfide bonds (S-S) are introduced into the main chain of the epoxy resin, and monomers with a diazafluorene structure and a disulfide bond structure are adopted as reactants, so that the dynamic self-healing antirust epoxy resin has an effect of self-healing micro-region defects and damages generated in a coating, and can inhibit corrosion exacerbation of damaged parts, effectively prevent the micro-region defects from further expanding to form cracks, improve the service performance of the resin and the coating, prolong the service life of a protective object, can be used for preparing anticorrosion and functional coatings, can autonomously heal and repair the micro-damages and micro-defects of the coating without external stress, illumination, high temperature and other conditions, and has the effects of enhancing the corrosion protection effect of the coating and prolonging the service life of the coating.
Description
Technical Field
The invention relates to the field of antirust epoxy resin, in particular to dynamic self-healing antirust epoxy resin and a preparation method thereof.
Background
The service life of marine ships and equipment in China is seriously affected by corrosion under severe environments such as high temperature, high humidity, high salt, strong ultraviolet rays and the like, and the traditional protective primer is easy to generate microscopic defects such as cracks, bubbles, pinholes and the like in the coating and using processes, and the microscopic defects can cause direct contact of a metal substrate and a corrosion medium to cause local corrosion, expand corrosion areas, seriously affect the corrosion protection period of a coating and shorten the service life of equipment. The traditional coating repairing modes such as repairing and welding can only repair macroscopically, damage cannot be repaired microscopically, and frequent maintenance work also severely limits the fight force of weaponry in China.
The current self-healing method applied to the anti-corrosion coating is mainly explant self-healing, and is characterized in that a corrosion inhibitor is modified or introduced into a self-healing microcapsule technology, the corrosion inhibitor is compounded with a polymer matrix in the preparation process of the material, when the matrix is cracked, the microcapsule is cracked to enable the repairing agent to flow out, and the crack is penetrated to enable the repairing agent to heal again. The technology aims at the problem that the existing microcapsule has low contact rate of a repairing agent and a curing agent, poor dimensional matching of the self-repairing microcapsule and a coating, difficult realization of effective repair of the coating crack on the micrometer scale of the microcapsule, and the like. In addition, as the self-healing agent is required to be introduced in the explant type self-healing process, the material is irrepeatable in repairing, irreversible and can not ensure the safety and the service life of the material, and the self-healing effect and the practical application of the coating material are affected. In addition, in the prior art, a technology for promoting the self-repairing of the epoxy resin by utilizing the reversible characteristic of the disulfide bond also exists, but in the prior art, a chain extender or a curing agent with the disulfide bond is added on the basis of a finished epoxy resin structure, the disulfide bond cannot be added into a resin main chain, the disulfide bond cannot be uniformly distributed in the epoxy resin main chain, so that the added disulfide bond has extremely limited effect of promoting the self-healing of the epoxy resin, and the use requirement of the self-healing of the epoxy resin cannot be met.
Disclosure of Invention
The invention aims to provide a dynamic self-healing antirust epoxy resin and a preparation method thereof, which can be used for preparing an anticorrosive coating, have an effect of self-healing micro-region defects and damages generated in the coating, and can inhibit the corrosion aggravation of damaged parts, effectively prevent the micro-region defects from further expanding to form cracks, improve the service performance of the resin and the coating and prolong the service life of a protected object.
The technical scheme adopted by the invention for solving the technical problems is as follows: a dynamic self-healing antirust epoxy resin has the structural formula:
wherein m, x and n are integers.
The preparation method of the dynamic self-healing antirust epoxy resin comprises the following steps:
step one, weighing according to parts by weight: dinitrogen bisphenol fluorene: 1-15 parts of dithiodiacid: 10-20 parts of epoxy chloropropane: 60-65 parts of catalyst: 1-2 parts of solid sodium hydroxide: 2-10 parts of solid sodium hydroxide which is weighed is prepared into sodium hydroxide aqueous solution;
adding the diazabisphenol fluorene, dithiodiacid and the catalyst which are weighed in the first step into epichlorohydrin, and simultaneously adding an organic high-boiling-point polar solvent into epichlorohydrin, and stirring until reactants are dissolved and uniformly mixed to obtain a mixed reactant;
step three, heating the mixed reactant in the step two to 100-120 ℃ and stirring, and preserving heat for 20-60 minutes to perform ring-opening reaction; then cooling to 25-30 ℃, adding the sodium hydroxide aqueous solution prepared in the first step, continuously stirring, and preserving heat for 5-10 hours to perform a ring-closure reaction to obtain a mixed solution containing a resin product;
and step four, continuously adding toluene into the mixed solution in the step three until the mixed solution is split, washing the split mixed solution to be neutral by using deionized water, and then carrying out water removal treatment and reduced pressure distillation to remove residual epichlorohydrin and organic high-boiling-point polar solvent in the mixed solution, thereby obtaining the dynamic self-healing antirust epoxy resin.
Preferably, the reaction route of the epoxy resin is as follows:
wherein m, x and n are integers.
Preferably, the diazabisphenol fluorene has a diazafluorene structure and two phenolic hydroxyl groups, and the molecular formula is:
preferably, the disulfideThe substituted diacid is aliphatic diacid containing disulfide bonds, and the structural formula is as follows:
wherein x is an integer and x is more than or equal to 1 and less than or equal to 5.
Preferably, the catalyst is a quaternary ammonium salt phase transfer catalyst.
Preferably, the catalyst is one or more of benzyl triethyl ammonium bromide, tetrabutyl ammonium bromide and tetrabutyl ammonium chloride.
Preferably, the organic high-boiling-point polar solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone.
Preferably, the mass concentration of the sodium hydroxide aqueous solution is 30% -50%.
According to the invention, disulfide bonds (S-S) are introduced into the main chain of the epoxy resin, when the epoxy resin is damaged, the disulfide bonds are broken under the conditions of stress and the like to form sulfur free radicals, so that sulfydryl is formed, and external energy is released in the state to prevent the coating from being further damaged; meanwhile, the broken chain segments are connected again to form disulfide bonds again, so that the self-healing effect is achieved.
The invention adopts the monomer with the diazafluorene structure and the disulfide bond structure as the reactant, so when the epoxy resin is used as the coating of metal equipment, the diazafluorene structure of the epoxy resin and free Fe on the surface of the metal equipment 2+ Can generate chelation reaction to reform a stable five-membered ring structure, thereby avoiding free Fe on the surface of metal equipment 2+ Rust formation, fixing free Fe 2+ Effectively prevent the corrosion process and play a role in rust prevention.
According to the invention, the self-healing effect and the antirust effect of the epoxy resin are comprehensively utilized in the repair and corrosion inhibition of the coating, when the coating is damaged in the initial stage, micro cracks are mainly generated, and disulfide bonds (S-S) are reconnected among broken chain segments and are formed again to perform self-healing of the coating; when the damage of the coating further expands, the external corrosive medium can invade the surface of the metal equipment and then the metalThe surface of the device generates free Fe through electrochemical reaction 2+ The "diazafluorene" structure is capable of reacting with free Fe by chelation 2+ And (3) reforming a stable five-membered ring, and forming a chelate bond to further strengthen a polymer chain segment so as to realize coating repair and corrosion inhibition.
According to the technical scheme, the invention has the beneficial effects that:
according to the invention, disulfide bonds are used as reversible covalent bonds, and non-covalent bonds are directly introduced into epoxy resin polymer molecules, so that the self-repairing epoxy resin material with dynamic self-healing performance is obtained, the self-repairing epoxy resin material can be used for preparing anti-corrosion and functional coatings, and can automatically heal and repair the micro-damage and micro-defect of the coating without additional stress, illumination, high temperature and other conditions, and has the beneficial effects of enhancing the corrosion protection effect of the coating, prolonging the service life of the coating and the like.
Compared with the prior art, the invention takes the disulfide bond structure as a monomer in the synthesis process, realizes the uniform distribution of the disulfide bond in the epoxy resin main chain, overcomes the defect that disulfide bonds are difficult to be added into the resin main chain and cannot be uniformly distributed in the epoxy resin main chain in the prior art, greatly improves the promotion effect of the disulfide bonds on the self-healing of the epoxy resin, and also introduces the diazofluorene structure with the chelating function into the epoxy resin main chain by a method of enabling the diazo bisphenol fluorene monomer to participate in polymerization, so that the self-healing epoxy resin has multiple self-healing composite mechanisms, can be respectively repaired aiming at different stages of coating damage and corrosion expansion, has the repairing efficiency improved by 50 percent to 70 percent and has good-application effect compared with the single healing mechanism.
Detailed Description
The invention provides a dynamic self-healing antirust epoxy resin, which has the structural formula:
wherein m, x and n are integers.
The invention also provides a preparation method of the dynamic self-healing antirust epoxy resin, which comprises the following steps: step one, weighing according to parts by weight: dinitrogen bisphenol fluorene: 1-15 parts of dithiodiacid: 10-20 parts of epoxy chloropropane: 60-65 parts of catalyst: 1-2 parts of solid sodium hydroxide: 2-10 parts of solid sodium hydroxide which is weighed is prepared into sodium hydroxide aqueous solution.
And step two, adding the dinitrogen bisphenol fluorene, dithio diacid and the catalyst which are weighed in the step one into epichlorohydrin, and simultaneously adding an organic high-boiling-point polar solvent into epichlorohydrin, and stirring until the reactants are dissolved and uniformly mixed to obtain a mixed reactant.
Step three, heating the mixed reactant in the step two to 100-120 ℃ and stirring, and preserving heat for 20-60 minutes to perform ring-opening reaction; then cooling to 25-30 ℃, adding the sodium hydroxide aqueous solution prepared in the step one, continuously stirring, and preserving heat for 5-10 hours to perform a ring-closure reaction to obtain a mixed solution containing a resin product.
And step four, continuously adding toluene into the mixed solution in the step three until the mixed solution is split, washing the split mixed solution to be neutral by using deionized water, and then carrying out water removal treatment and reduced pressure distillation to remove residual epichlorohydrin and organic high-boiling-point polar solvent in the mixed solution, thereby obtaining the dynamic self-healing antirust epoxy resin.
The reaction route of the epoxy resin in the reaction is as follows:
wherein m, x and n are integers.
The diazabisphenol fluorene has a diazafluorene structure and two phenolic hydroxyl groups, and the molecular formula is:
the dithiodiacid is aliphatic diacid containing disulfide bonds, and has the structural formula:
Among various reactants, the catalyst adopts quaternary ammonium salt phase transfer catalyst, and can specifically adopt one or more of benzyl triethyl ammonium bromide, tetrabutyl ammonium bromide and tetrabutyl ammonium chloride; the organic high boiling point polar solvent can be one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone; the mass concentration of the sodium hydroxide aqueous solution is 30-50%.
Example 1
According to the mass portion, 5 portions of diazabisphenol fluorene, 20 portions of dithiodipropionic acid and 1 portion of tetrabutylammonium bromide serving as a catalyst are added into 65 portions of epichlorohydrin, simultaneously N, N-dimethylformamide solvent is added for stirring and dissolving, the mixed reactant is heated to 100 ℃ and stirred for reacting for 20 minutes, then the mixed reactant is cooled to 25 ℃, 50% sodium hydroxide aqueous solution (containing 9 portions of solid sodium hydroxide) with mass concentration is slowly added, and stirring and reacting are carried out for 6 hours to obtain a mixed solution. And continuously adding toluene into the mixed solution until the mixed solution is split, washing the mixed solution to be neutral by using deionized water, adding a solid water absorbent to remove water, and removing residual epichlorohydrin and organic high-boiling-point polar solvent in the mixed solution by vacuum distillation at 110 ℃ to obtain the dynamic self-healing antirust epoxy resin.
The dynamic self-healing antirust epoxy resin is reddish brown viscous liquid with an epoxy value of 0.24, and is mixed and cured with polyamide curing agent to obtain reddish brown varnish film, the varnish film is cut by a knife and then the kerfs are closely contacted, the resin is placed for 6 hours at normal temperature, and a good self-healing effect is achieved at resin fracture parts.
Examples 2 to 4
The specific procedure is as in example 1, wherein the feed quality of each monomer of diazobisphenol fluorene, dithiodipropionic acid and epichlorohydrin is as follows:
| examples | Dinitrogen bisphenol fluorene | Dithiodipropionic acid | Epichlorohydrin |
| 2 | 10 | 20 | 60 |
| 3 | 15 | 15 | 60 |
| 4 | 5 | 20 | 65 |
The self-healing antirust epoxy resin prepared in the examples 1-4 is uniformly brushed on a sand-blasted carbon steel plate after being mixed with a polyamide curing agent, the dry film thickness is about 50 mu m, after being sealed, the self-healing antirust epoxy resin is placed in a salt spray box for 600 hours for salt spray test, the surfaces of paint films are all intact, the base materials are free from rust, and the epoxy resins prepared in the examples 1-4 have good antirust performance.
Claims (9)
1. The dynamic self-healing antirust epoxy resin is characterized by comprising the following structural formula:
wherein m, x and n are integers.
2. The method for preparing the dynamic self-healing antirust epoxy resin in claim 1, which is characterized by comprising the following steps:
step one, weighing according to parts by weight: dinitrogen bisphenol fluorene: 1-15 parts of dithiodiacid: 10-20 parts of epoxy chloropropane: 60-65 parts of catalyst: 1-2 parts of solid sodium hydroxide: 2-10 parts of solid sodium hydroxide which is weighed is prepared into sodium hydroxide aqueous solution;
adding the diazabisphenol fluorene, dithiodiacid and the catalyst which are weighed in the first step into epichlorohydrin, and simultaneously adding an organic high-boiling-point polar solvent into epichlorohydrin, and stirring until reactants are dissolved and uniformly mixed to obtain a mixed reactant;
step three, heating the mixed reactant in the step two to 100-120 ℃ and stirring, and preserving heat for 20-60 minutes to perform ring-opening reaction; then cooling to 25-30 ℃, adding the sodium hydroxide aqueous solution prepared in the first step, continuously stirring, and preserving heat for 5-10 hours to perform a ring-closure reaction to obtain a mixed solution containing a resin product;
and step four, continuously adding toluene into the mixed solution in the step three until the mixed solution is split, washing the split mixed solution to be neutral by using deionized water, and then carrying out water removal treatment and reduced pressure distillation to remove residual epichlorohydrin and organic high-boiling-point polar solvent in the mixed solution, thereby obtaining the dynamic self-healing antirust epoxy resin.
3. The method for preparing the dynamic self-healing antirust epoxy resin according to claim 2, wherein the reaction route of the epoxy resin is as follows:
wherein m, x and n are integers.
4. The method for preparing the dynamic self-healing antirust epoxy resin according to claim 2, which is characterized in that: the diazabisphenol fluorene has a diazafluorene structure and two phenolic hydroxyl groups, and the molecular formula is as follows:
5. the method for preparing the dynamic self-healing antirust epoxy resin according to claim 2, which is characterized in that: the dithio diacid is aliphatic diacid containing disulfide bonds, and the structural formula is as follows:
wherein x is an integer and x is more than or equal to 1 and less than or equal to 5.
6. The method for preparing the dynamic self-healing antirust epoxy resin according to claim 2, which is characterized in that: the catalyst adopts quaternary ammonium salt phase transfer catalyst.
7. The method for preparing the dynamic self-healing antirust epoxy resin according to claim 5, which is characterized in that: the catalyst is one or more of benzyl triethyl ammonium bromide, tetrabutyl ammonium bromide and tetrabutyl ammonium chloride.
8. The method for preparing the dynamic self-healing antirust epoxy resin according to claim 2, which is characterized in that: the organic high-boiling-point polar solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone.
9. The method for preparing the dynamic self-healing antirust epoxy resin according to claim 2, which is characterized in that: the mass concentration of the sodium hydroxide aqueous solution is 30% -50%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2016034621A (en) * | 2014-08-04 | 2016-03-17 | 日塗化学株式会社 | Repair coating method for steel structure |
| WO2017147940A1 (en) * | 2016-02-29 | 2017-09-08 | 宏昌电子材料股份有限公司 | Preparation process for 4,4'-(9-fluorenylidene)diphenol epoxy resin |
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| US4980234A (en) * | 1987-12-23 | 1990-12-25 | Minnesota Mining And Manufacturing Co. | Epoxide resin compositions and method |
| US9701797B2 (en) * | 2015-10-16 | 2017-07-11 | GM Global Technology Operations LLC | Self-healing carbon fiber composites |
| CN109233571B (en) * | 2018-10-12 | 2021-01-15 | 南宁本吉生物科技有限公司 | Solvent-free self-repairing epoxy resin and preparation method thereof |
| CN109400848B (en) * | 2018-10-23 | 2021-04-27 | 福州大学 | Synthesis of fluorenyl epoxy resin and application of fluorenyl epoxy resin in thermosetting resin |
| CN109608985B (en) * | 2018-12-08 | 2020-11-06 | 郑州师范学院 | Anticorrosive coating capable of being automatically repaired and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016034621A (en) * | 2014-08-04 | 2016-03-17 | 日塗化学株式会社 | Repair coating method for steel structure |
| WO2017147940A1 (en) * | 2016-02-29 | 2017-09-08 | 宏昌电子材料股份有限公司 | Preparation process for 4,4'-(9-fluorenylidene)diphenol epoxy resin |
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| Title |
|---|
| 仿生自修复环氧树脂涂层制备及性能;廖乐平;张伟;赵阳;;中国表面工程(第04期);全文 * |
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